Reactive monoazo pyrazolone dyes



United States Patent US. Cl. 260-153 8 Claims ABSTRACT OF THE DISCLOSURE Reactive dyes of the formula HO N-A Rr-N H-Y-N H-O C N N biT (1) wherein R is a reactive group,

R is hydrogen, lower alkyl or chlorine,

R is lower alkyl, --COOH, COO-lower alkyl or optionally substituted -CO-NH A is a benzene or naphthalene radical containing at least one SO H group and if desired further substituents and Y isone of the radicals This invention relates to reactive dyes of the formula I where R stands for an acyl radical which bears at least one substituent cleavable as an anion and/or a CC multiple linkage capable of additive reaction, or for a halogenopyrimidyl or halogenotriazinyl radical,

'R for hydrogen, lower alkyl (e.g. methyl) or chlorine,

R for lower alkyl, COOH, COO-lower alkyl, or optionally substituted CONH A for a benzene or naphthalene radical containing at least one sulfonic acid group and if desired further substituents, and

Y torque of the following radicals 3,542,753 Patented Nov. 24, 1970 ice The process for the production of the reactive dyes of the Formula I consists in reacting the diazo compound of an amine of formula where R, has one of the aforecited meanings of R or stands for a non-reactive acyl radical, with a pyrazolone of formula (III) N so that coupling takes place in ortho-position to the enolic hydroxyl group, after which, when R, stands for a non-reactive acyl radical, the resulting monoazo dye is de-acylated and reacted with an acylating agent containing at least one substituent cleavable as an anion and/ or a CC multiple linkage capable of additive reaction, or with a polyhalogenopyrimidine or polyhalogenotriazine.

When R is an acyl radical containing at least one substituent cleavable as an anion and/or a CC multiple linkage capable of additive reaction, it may be, e.g., the

radical of a lower aliphatic acid bearing at least one halogen atom or one group cleavable as an anion, such as Br, cl or --OSO H, and/or a CC double bond capable of additive reaction; such acids are, e.g., chloroacetic, bromacetic, ,B-chloropropionic, fi-bromopropionic, 0a,}3-di6hlOIOPfOPlOIliC, a,B-dibromopropionic, acrylic, methacrylic, a-chloracrylic, u-bromacrylic, 'y-chlorocrotonic, 'y-bromocrotonic, 0:,{3- and [3,,8-dichloroacrylic, 0a,}?- or {3,B-dibromoacry1ic, trichloroacrylic, tribromoacrylic, fi-chloroethyl-sulfonic, B-bromoethyl-sulfonic, fl-sulfatopropionic, fi-sulfatoethylsulfonic, vinylsulfonic, B-methylsulfonyloxy-, fi-phenylsulfonyloxyor /8-(4-methy1phenyl sulfonyloxy)-propionic acid; R may also be the radical of a halogenated heterocyclic acid, e.g. 2,4-dichloroor 2,4-dibromopyrimidine-S-carboxylic acid, 2,4-dichloroor 2,4-dibromo 6 methylor -6-chloromethylpyrimidine-5- carboxylic acid, 2,3-dichloroor 2,3-dibromoquinoxaline- 5- or -6-carboxylic acid or -sulfonic acid, 2(3)-monobromoor 2(3)-monoch1oroquinoxaline-6-carboxylic acid, 1,4-dibromoor 1,4 dichlorophthalazine 6 carboxylic acid, 2-bromoor 2-chlorobenzoXazole-5, -6- or -7-carboxylic acid, Z-bromoor 2-chlorobenzothiazole-S-carboxylic acid or -6-sulfonic acid, 3- or 4-(4',5-dichloroor (4',5 '-dibromo-6-pyridazonyl 1' -benzene-1-carboxylic acid or fi-(4,5'-dichloroor -(4',5-dibromo-6-pyridazonyl-l)-propionic acid. When R is a halogenopyrimidyl or halogenotriazinyl radical, it is, e.g., the radical of a polyhalogenopyrimidine or polyhalogenotriazine contain ing at least two mobile halogen atoms, e.g. the radical of cyanuric chloride or cyanuric bromide or the primary condensation products of a cyanuric halide of formula H which may be further substituted, of a primary or secondary aliphatic, alicyclic, aromatic or heterocyclic amine, an aliphatic, alicyclic, aromatic or heterocyclic hydroxyl or thiol compound, in particular the radical of aniline, its alkyl, sulfonic acid or carboxylic acid derivatives, of am monia, lower monoalkylamines or dialkylamines; the radical of 2,4,6-trichloropyrimidine, 2,4,6-tribromopyridine and their derivatives which may bear the following substituents in the 5-position: methyl, ethyl, cyano, carboxy, carboxylic acid methyl or ethyl ester, chlorovinyl, substituted alkyl, e.g. carboxymethyl, chloromethyl or bromomethyl; the radical of 2,4,5,6-tetrachloroor -tetrabromopyrimidine, S-bromo 2,4,6 trichloropyrimidine, 2,4-dichloro-S-chloromethylor 2,4-dibromo-5-bromomethylpyrimidine, 2,4-dichloro-5-chloromethyl-6-methylor 2,4- dibromo-S-bromomethyl-6-methylpyrimidine.

The substituent R stands preferably for methyl, ethyl, carboxyl, COOCH -COOC H -CONH CONHCH CO-NHC H -CONHC H CONH--C H OH, CO-N (CH The aryl radical A containing at least one sulfonic acid group may be, e.g., 2-, 3- or 4-sulfophenyl, 2,4-, 2,5- or 3,5-disulfophenyl, 2-methyl-4- or -5-sulfophenyl, 2-chloro- 4- or -5-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2,3,6-trichloro-S-sulfophenyl, Z-methyl-6-chloro-4-sulfophenyl, 4- methylor 4-chloro-2-sulfophenyl, 4-, 6- or 7-sulfonaphthyl-l, 3,6-, 4,6-, 4,7- or 5,7-disulfonaphthyl-l, 5-, 6-, 7- or 8-sulfonaphthyl-2, 4,7-, 4,8-, 5,7- or 6,8-disulfonaphthyl-Z.

The amine of Formula II can be diazotized by the direct or indirect method at to 30 C., or preferably at 1520 C. The coupling reaction with the pyrazolone of Formula III is best effected at 0 to 40 C. or preferably at 15-25 C. and at a pH of to 12 or preferably 7 to 10, the alkali required for neutralization being preferably added gradually in small portions.

When the radical R in the amine of Formula II stands for a reactive radical R the dye can be precipitated, e.g. by the addition of salt, and then filtered off, washed with salt solution and dried.

When the radical R in the amine of Formula II represents a non-reactive acyl radical, it is split off by hydrolysis. Cleavage can be effected in mineral acid medium, e.g. in 2 to 6% hydrochloric or sulfuric acid solution, or in alkaline medium, e.g. 1 to 5% sodium hydroxide or potassium hydroxide solution, at temperatures from 70 C. to the boiling point of the solution.

An aqueous medium is best suited for reacting the aminoazo dye and the reactive component. To introduce the aliphatic acyl radicals that bear at least one substituent cleavable as an anion and/or a C-C multiple linkage capable of additive reaction, it is convenient to employ the acid halides or anhydrides or isocyanates and to work with good cooling in the presence of an acidbinding agent, e.g. sodium carbonate, sodium hydroxide, barium hydroxide, calcium hydroxide or sodium acetate.

The carboxylic acid halide employed for acylation can be added as it is or it can be dissolved in two to five times its amount of an inert organic solvent such as benzene, chlorobenzene, methylbenzene, dimethylbenzene or acetone, and the solution dropped into the aqueous solution of the compound bearing the amino group at 0 to 30 C. or preferably about 25 C. in the presence of an acidbinding agent, preferably at pH 7 to 3.

For the carboxylic acid or sulfonic acid halides of the halogenated heterocyclic compounds the temperatures may vary from 0 to 100 C., e.g. 0 to 50 C. or preferably, 0 to 25 C. for the 2,4-dihalogenopyrimidine-S-carboxylic acid halides, about to 50 C. or preferably to 30 C. for the 3- or 4-(4',5'-dihalogeno-6'-pyridazonyll)-benzene-carboxylic acid chlorides or the fl-(4,5'-dihalogeno 6' pyridazonyl-1')-propionic acid chlorides, about 20 to 90 C. for the halogenoquinoxaline, -phthalazine-, -benzoxazoleor -benzothiazole-carboxylic acid chlorides or-sulfonic acid chlorides, and preferably about 30 to 70 C. for the 2,3-dihalogenoquinoxaline-S- or 6- carboxylic acid chloride or -6-sulfonic acid chloride. The reaction is conducted advantageously in a weakly alkaline, neutral to weakly acid medium, preferably within the pH range of 7 to 3, e.g. pH 6 to 4.

The reaction with the polyhalogenopyrimidines or polyhalogenotriazines is also carried out in aqueous medium. The halide can be employed as it is or in solution in an organic inert solvent, suitable solvents for this purpose being acetone, chloroform, benzene, chlorobenzene and toluene.

The reaction temperature is adjusted to the reactivity of the starting products and varies from 0 to C. It may be 0 to 20 C. for cyanuric chloride and cyanuric bromide, 3050 C. for the monocondensation products containing two mobile halogen atoms obtained with cyanuric chloride or bromide and ammonia, a primary or secondary amine, an alcohol, thioalcohol, phenol or thiophenol, or 20100 C. for the polyhalogenopyrimidines. If temperatures higher than about 40 C. have to be employed it is advisable to work in a vessel fitted with a reflux condenser, in view of the volatility of halogenopyrimidines in water vapour. The reaction can be carried out in weakly alkaline, neutral to weakly acid medium, but the pH region of 7 to 3 is preferable.

To maintain a constant pH value during the reaction of the aminoazo dye with the reactive component, an acidbinding agent such as sodium acetate can be added to the reaction solution at the commencement of the operation, or sodium or potassium carbonate or bicarbonate in solid pulverized form or in concentrated aqueous solution can be added in small portions in the course of the reaction. Aqueous solutions of sodium or potassium hydroxide are other suitable neutralizing agents.

The addition of small amounts of a wetting or emulsifying agent can accelerate the rate of reaction.

The monoazo dyes formed can be precipitated from their aqueous solutions or suspensions with salt, filtered off, washed with salt solution if necessary, and dried.

Especially interesting dyes are those of the formula wherein R R and Y have the aforecited meanings and A represents monoor disulfophenyl, monoor disulfonaphthyl, methyl-sulfophenyl, monochloro-, dichloroor trichlorosulfophenyl or methyl-chlorosulfophenyl and R represents the radical of a lower aliphatic acid bearing at least one halogen atom or one group cleavable as an anion and/or a C-C double bond capable of additive reaction, such radicals being e.g. lower monoor dihalogenoalkanoyl, lower alkenoyl, lower mono-, dior trihalogenoalkenoyl, lower sulfate-alkanoyl, lower alkanesulfonyloxy-lower alkanoyl, mono-nuclear arylsulfonyloxylower alkanoyl, lower monohalogeno-alkylsulfonyl, lower sulfatoalkylsulfonyl, lower alkenylsulfonyl; the radical of a halogenated heterocyclic acid containing one nitrogen atom and a second hetero atom selected from. the group consisting of nitrogen, oxygen and sulfur and in which the halogen atom or atoms are bound to carbon atoms of the heterocyclic ring, such radicals being e.g. 2,4-dihalogenopyrimidyl-S-carbonyl, 2,4 dihalogeno 6- methylpyrimidyl-S-carbonyl, 2,3-dihalogenoquinoxalyl-5- carbonyl, -6-carbonyl, -6-sulfonyl or -6-aminocarbonyl, 2(3 )-monohalogenoquinoxalyl 6 carbonyl, 1,4-dihalogeno-phthalazyl-6-carbonyl, 2 halogenobenzoxazolyl-5-, -6- or -7-carbonyl, 2-halogenobenzothiazolyl-S-carbonyl or -6-sulfonyl, 3- or 4-(4,5'-dihalogeno-6-pyridazonyl-1)- benzene-l-carbonyl or )3-(4, 5'-dihalogeno-6-pyridazonyll')-propionyl; the radical of a polyhalogenopyrimidine, e.g. mono-, dior trihalogenopyrimidyl, 2,4-dihalogenopyrimidyl-S-methylene or 2,4-dihalogeno-6-methylpyrimidyl-Snnethylene; the radical of a polyhalogenotriazine, e.g. 4,6-dihalogeno-1,3,5-triazinyl 2,4 lower alkoxy-6- halogeno-1,3,5-triazinyl-2, 4-mononuclear aryloxy-6-halogeno-l,3,5-triazinyl-2, 4-amino-6-halogeno-1,3,5-triazinylthe dyes of the formula 10 wherein A represents 3- .or 4-sulfophenyl, 2,4-, 2,5- or 3,5-disulfophenyl, 2-chloro-4- or -'5-sulfophenyl, 2-methyl-4- or -5-sulfophenyl, 2,5-dichloro-4-sulfophenyl or 2-chloro-6- methyl-4-sulfophenyl and R represents 2,6-dichloro-pyrimidyl-4, 4,6-dichloropyrimidyl-2, 2,5,6-trichloropyrimidyl-4, 2,4-dichloro-6- methyl-pyrimidyl-S-methylene, 4,6-dichloro 1,3,5 triazinyl-Z, 6-chloro-4-amino-1,3,5-triazinyl-2, 6 chloro 4- methylaminol ,3 ,5 -triazinyl-2, 6-chloro-4-methoxy-l ,3 ,5 triazinyl-Z, 6-chloro-4-(3'- or 4-sulfophenylamino)-1,3,5- triazinyl-Z, fl-chloropropionyl, acryloyl, a-chloroor 06-- bromoacryloyl, [3- (4',5'-dichloro-6'-pyridazonyl-1' -propionyl, 2,3-dichloroquinoxalyl-6-carbonyl or 2-chlorobenzothiazolyl-6-sulfonyl.

The new reactive dyes have good substantivity, i.e. affinity for cellulosic fibers, good stability to hard water and good compatibility with salt. They dissolve well in water, which permits them to be applied at a liquor to goods ratio of 10:1 or in many cases 3:1, while the unfixed pro portion of dye can be easily washed off after dyeing. The dyes are well stable to lengthy boiling times in the dyebath, are stable to alkalis and not appreciably sensitive to reducing influences. In an alkaline bath they cover barry viscose rayon, and from acid baths they dye wool, silk and polyamide fibers. They reserve polyester, polyacrylonitrile, polyvinyl chloride, cellulose-triacetate and polyalkylene fibers. The dyes are well suitable for dyeing or padding wool, silk, polyamide fibers, natural and regenerated cellulosic fibers, e.g. cotton, linen, viscose filament yarn, viscose staple fibers and cuprammonium rayon, etc. and blends of these fibers. They are also suitable for leather. The optimum conditions of application are governed by the nature of the fiber and the dyes used. Animal and polyamide fibers can be dyed or fixed in an acid, neutral or weakly alkaline medium, e.g. in the presence of acetic, formic or sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. Dyeing can be carried out in an acetic acid to neutral bath in the present of levelling agents, e.g. polyoxyethylated fatty amines or mixtures of these and alkylpolyglycol ethers, and the bath adjusted to a neutral or weakly alkaline reaction at the end of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium carbonate or bicarbonate, or of compounds which react neutral on heating, e.g. hexamethylene tetramine or urea. Subsequently the goods are rinsed well and if necessary acidified with acetic acid. The dyeings obtained are of brilliant greenish yellow to reddish yellow shade and have good light fastness in the dry and wet states, together with very good fastness to wet tests such as water, water spotting, washing, milling, perspiration, wet rubbing and acid cross dyeing. They withstand acid vapours, sulfurous acid and even strong acids such as sulfuric acid, and are fast to dry cleaning.

An alkaline medium is preferable for the dyeing, padding or fixation of the dyes on cellulosic fibers; suitable alkalis include sodium carbonate and bicarbonate, sodium or potassium hydroxide solution, sodium metasilicate,

sodium borate, tri-sodium phosphate, ammonia. It is often of advantage to add a mild oxidizing agent, e.g., sodium 1-nitrobenzene-3-sulfonate, to the dyeing or padding medium to obviate reduction effects. Dyeings on cellulosic fibers can be fixed at room temperature or with heating, depending on the reactive group of the dye.

The dyeings on cellulosic fibers have extremely good wet fastness properties owing to the formation of a stable chemical linkage between the dye molecule and the cellulose molecule.

Often the total amount of dye applied does not take part in the chemical reaction with the fiber. In these cases the unreacted proportion of dye is removed by suitable treatment, such as rinsing and/or soaping, if necessary at high temperature. For this purpose synthetic detergents can be used, e.g. alkylarysulfonates such as sodium dodecylbenzenesulfonate, alkylsulfates such as sodium cetyl sulfate or sodium lauryl sulfate, or alkyl-, monoalkylphenylor dialkylphenylpoly-glycol ethers which may be sulfated or carboxymethylated, such as sodium lauryl polyglycol ether sulfate.

Brilliant yellow dyeings of good tinctorial strength are obtained which have good fastness to light in the dry and wet states and very good fastness to wet tests such as Water, water spotting, washing, perspiration, soda boiling, alkali, wet rubbing, and acid cross dyeing. They show good stability to acid vapours, sulfurous acid and even strong acids such as sulfuric acid, and are fast to dry cleaning and stable to resin finishes.

The new dyes can be combined with other reactive dyes, e.g. blue anthraquinone, red azo or turquoise copper phthalocyanine dyes, to produce yellow-red, blue or green dyeings. These combination dyeings are not subject to catalytic fading and have very good light fastness in the wet state.

The dyes of the present invention have better light fastness than the next comparable dyes disclosed in British patent specifications Nos. 852,120 and 828,35 3, which do not contain the bridge In the following examples the parts and percentages are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 42.5 parts of 4-(3"-aminobenzoylamino)-4'-acetylami no-l,1-diphenyl-3-sulfonic acid are suspended in 600 parts of water and 15 parts of 30% hydrochloric acid at 20 with thorough stirring and are diazotized with 6.9 parts of sodium nitrite. 35 parts of sodium l-(2'-chlorophenyl)- 3-methyl-5-pyrazolone-5-sulfonate are added, and subsequently 20 parts of sodium carbonate to effect coupling. The dye thus formed is suspended in the demium, but on heating to 90 it goes into solution, on which 130 parts of 30% hydrochloric acid are added and the soluton stirred for 1 hour at -90 to carry out the deacetylation. The aminomonoazo dye is then filtered off with suction and dissolved in 700 parts of Water at and at a pH value of 7. At the same temperature 22 parts of 2,4,5,6- tetrachloropyrimidine are added with stirring, and the pH value is then maintained at 6-7 by dropping in sodium carbonate solution until the condensation reaction is complete. The dye is precipitated by the addition of sodium chloride, filtered off and dried. On grinding it is obtained as a yellow powder which dissolves in water with a greenish yellow colour.

7 8 DYEING METHOD EXAMPLE 4 A dyehath is prepared with 2 parts f the dye f 41.6 parts of the disodium salt of the amino dye of ample 1 in 4000 parts of softened water at 40. 100 parts Formula IX are surfed at room temperature-1M0 600 P F of a cotton fabric, mercerized and previously wetted out, of wfiter contalnlng p gts of 30 sodium hydroxide are entered into the bath, after which 110 parts of calcined 5 AftFr 9 8 to O a 501mm of Parts of Y sodium sulfate and 30 parts of calcined sodium carbonate arfuncfhlonde Parts of chloroform 15 d p are added The bath is raised to in 30 minutes, with with vigorous stirring. The temperature is maintained at a further 110 parts of calcined sodium sulfate added after and PH Value at 5.5-6.5 by dropwise addition 10 minutes and 100 parts after 20 minutes. On reaching 20% Carbonate? soluuong w h commuous the boil a final 50 parts of calcined sodium carbonate are 0 rmg unt1l no further ammo dye The final added and the bath is then held at the boil for 1 hour. dye 1S Salted out, filtered Off, Washed Wlth brme and The cotton is then removed, rinsed with water and dried; W driefli at grinding yellow Powder is it is dyed fast to light and Wet treatments in a greenish tamed wh1ch dissolves 1n water w1th a greenish yellow colyenow Shade our. To increase its stability the powder dye is mtrmately EXAMPLE 2 15 mixed with 10 parts of a phosphate buffer having a pH value of 7.0. 63.5 parts of the amino compound of formula Dyeing method C The dyebath is prepared with 2 parts of the dye of this L! example dissolved in 3000 parts of softened water at 40. SIOSNa sloaNa 100 parts of a previously wetted out fabric of cotton or vlscose rayon are entered into the bath, which is then (v11) raised to 60 over minutes with the gradual addition of 100 parts of calcined sodium sulfate. At this point 6 parts of sodium hydrogen carbonate are added and the bath is held at 60 for a further 30 minutes. Then 6 parts of calcined sodium carbonate are added in portions over 10 minutes and the bath is maintained at 60 for a final 15 minutes. The fabric is removed, rinsed with hot water, 30 soaped at the boil with a 0.3% solution of a non-ionic detergent, rinsed again and dried. A greenish yellow dyeing fast to light and wet treatments is obtained.

are suspended in 500 parts of water and 30 parts of 30% hydrochloric acid. The compound is diazotized at 20 with 25 6.9 parts of sodium nitrite, following which parts of sodium 1 (2-,5'-dichlorophenyl)-3-methyl-5-pyrazolone- 4'-sulfonate are added and the coupling reaction carried out with the addition of sodium carbonate. The dye is isolated as given in Example 1. It is a yellow powder which dissolves in water with a yellow colour and dyes cellulosic fibers by the dyeing method of Example 1 in greenish yellow shades of good light and wet fastness. EXAMPLE 5 41.6 parts of the disodium salt of the amino dye of EXAMPLE 3 35 Formula IX are reacted with 9.3 parts of cyanuric chlo- 115 P rts of the ammo compound o formula ride as described in Example 4. After the addition of a on -o OHNCH=CHNHO 0 1 (VIII) S OgNa S O Na are SllSPeHqed 250 0 Parts Of Wale? 1 62 P 0f 30% solution of 9.75 parts of sodium 1-aminobenzene-4-sulhyflrochlorlc acld Wlth thorough g- Ice 15 added fonate in 90 parts of water, the reaction mixture is stirred hung the temperature down to 15 and the compound is for a few hours at -50 with dropwise addition of 15% then diazotized with 13.8 parts of sodium nitrite. 68 parts odium rbo te l tion to maintain the pH value at of sodium 1 (2' chlorophenyl)-3-methyl-5-pyra 4.5 6.0-6.5. On completion of the reaction the monochlorotri- 4'- u1fonate are entered at 15-20 and coupling effected azine dye is salted out, filtered off and dried. Dyed on cotby the slOW addition of 40 parts Of sodium carbonate. The ton and regenerated cellulosic fibers by the method deresulting dye suspension is heated to 90, on which the dye scribed after Example 1, it gives greenish yellow dyeings. goes into solution. After the addition of 250 parts of 30% An identical dye is obtained when 41.6 parts of the dihydlochloric acid the Solutlon is Stirred for 1 hour at sodium salt of the amino dye of Formula IX are dissolved 8590. The aminomonoazo dye of formula in 600 parts of water at room temperature, the solution 01 r I HzNC OH=CH--NHO o- N=N 1h (IX) 03H g 0 11 in settles out in the form of the disodium salt. It is filtered combined with a solution of 17.5 parts of sodium 4-(4',6'- off, washed with brine and dried. dichloro-l',3',5-triazinyl-2-amino)-benzene 1 sulfo- 83.2 parts of the disodium salt of the aminomonoazo nate in 180 parts of water, and the reaction conducted by dye of Formula IX are dissolved in 750 parts of water stirring for a few hours at 45-50 with dropwise addition and 13.3 parts of 30% sodium hydroxide solution at 80. of 15 sodium carbonate solution to keep a constant pH 17.4 parts of 2,4,6-trichloropyrimidine are dropped in value of 5-6.

with stirring, and while the condensation reaction is in EXAMPLE 6 progress, 15% sodium carbonate solution is added to maintain the pH value at 5.5 to 6.5. The reaction is com- 41.6 parts of the disodium salt of the amino dye of plete when no further alkali is consumed. The dye is Formula IX are dissolved in 600 parts of water and 6.7 salted out, filtered off, washed with brine and dried. It is parts of 30% sodium hydroxide solution at 40-45. Into a yellow powder which dissolves in water with a yellow this solution is dropped a solution of 14 parts of 2,3-dicolour and gives greenish yellow dyeings of good light chloroquinoxaline-6-carboxylic acid chloride in 50 parts and wet fastness on cellulosic fibers. of benzene with vigorous stirring at 40-45 and with the The 2,4,6-trichloropyrimidine may be replaced by an addition of 15 sodium carbonate solution to maintain equivalent amount of 2,4,6-tribromopyrimidinc, on which the pH value at 66.5. When no further free amino group a similar dye is obtained. 76 is indicated, the dye is salted out, filtered off and vacuum Q am 0 82 swwwwwwmv 30 oh mwqwwh m s l. w zow NO W .4 ow EE Q W 53 6Q amo m wEEEEQBo oE 3 E QQ:= E QE Q m U ou 3cgno=5 hn Q Q N O w E EQEo Q QvQ o Q N O ou Q Q E AEQ Q Q m0 Hm w llll H fl wn fi zfiqm m l {Ill-lieu dm 6Q 50 m 2 w z fii m H-OE E EEQQEOEU N 3 8 38 :5 m0 m QE E EEC Q Q 42 5 63 Q "Z O m 2E2.5%dJ6 ENEE d Q "No i 65523 m EwR wE E Q +d I: Q "NO 525 0 EEEQE fii Q MO QES A mq fi kn w us w zwi Q 50 0555 3 Q EaE w h8o u o 6Q 3m 0 25050 23W E$Bo5o w 259 2333 m 0 32m Q Q N A m 655m a9652u+d hqwnnomcw Q 50 QEE m 2 asE hgn sn w d e 2 m0 wEEER vE d{ E :%a :w wa 6Q m 0 ou qaagnwfio d qfiw ou 33? m 0 HM w mA fib fi wqh 6 5Q 50 m 3 Ec ng: Q E B Q m 0 m ow hmwsnotzw ho gwb u .oQ m0 Engn wq 55:9 3350 m 0 .805? zwmcmm m W 0 W mm H1 0 w m 0 w an 50 m 52 2 2 526g N 43 %:5 :OI H IOI 2 "$88.6 "No Q $3830 3 2354 353 Q 50 m $5822 mq figo uim Q 3WD m i IIIII w mA nus fl ad Fowl: 6Q m 0 m :3 ?QE EoEd ghfisn o cwwqqw o 6Q m 0 H wflga wmoho u p i 6505A ou ou 3 .Eng 8 aifii afi aam 8 2 MO 8 Ahngnomn 96 w mfiam 6 m 0 m EW M O QE Qm 353 68 :0: w HQ 0 w .62 @353 i o H u nm "M "N .E E E M m M Euaq oumawflom .8 28:58 no $503. 05 o 095m 05 can can :4 m omvfi 05 mo mw qmofi 2t hp flonmmnmauwmu 93 25. S 8 H 3382mm 5 won owow 35 003 05 ba 2 3350 0.5 5 53 235cm 0 3% 38:05 3 0 3. 3am v3 mEBo ow 2 825 333:3 no augao 8B was u: o 3% mw owu 30m noch. 33m was .5200 30:9 a s. .535 5 338mm. 033 .BwBom Bozo a 3 3590 mm a 5 no wE-Bw v5 v3.6 e wououosm J wozmm mm 9nd 05 82m 88 mm uowmaoa 5 5 m 3 03? mm 0 Q E 8 uow om gon-Eu E uow 3 we qoumvwm $5.5m 05 an? t 23 ac 03 @38 0 0 o oEoEoHo ui mo .3m 3 was 0 o 3 200 mm Pav a 9 6533a 8 Soon an uou cw o xE E 8 3 0 55 was 5 we .53 can 8 @055 8a NH 225cm we 0% 038m 2: o 3% E uowmw 05 0 55 9:

Q who w E 253 a fisfi i aififing fisgd --fi i zii w m O H OI W O m 22 H252 U "m m -dignnbnfih o mB Bb Jd 3conQ:m m 3fioE m I Q mo fi o mz oo M E ESEWQ E EQm T Efi82 Q QHO HHZ OO QE ESA m H G E E 3 C wE v d Q @000 M 553 T28 22 2192523 n EthQE su w fim I .02 E000 EBEv 2 32: 525.fifl ggS o i ow 6Q HHOOO oEEEv Eon 3330.820 l 2 s w WOOD E dESEQ 3 Q W Q QQEE Q Efi23 8 u 1 2 52 6 5O QES Q 3 2 5553 0 n aofioh vi ow 1. 23? mooo fii E 3 2:2QEQi P WQEE n $53232 D E0 m 5282. E2 ozionoec m: QPE 4 1 5 2 6 50 m 6233a 33 2538a@ 28ww ha a Q Q mo 00 w 52 5 3.hfiwfifio io im Q JA O HHZ O 0 m E EE fifi fi{a 6 215 h Qmov Z o o w g twais tfiqflm 13230:: a D "m0 0351? no u o oflsm ow 5 "m0 $2850 23 3EEn 2 80 Q E O Q "m0 Q m 0 Q m 0 D "HMO Q "E O d n Er QR5ES {a 82 258 "m 0 E QS 3 6{m E= n= -2 Q O 0 0 23 3a95 Q E EEO Q 6 Q QE OVZ OO Q E o o 0 0 Q M2 0 O c cw 52 W O O O 3 monaw mafiE5 $4 0 afimcgn qvd anonqou m+ Q "m 0 m 25 25g m fioiififisnm oi mv aE o d o 0 m 0 m dfi tfifimJEBmEfiw B m d Q "E O m QESEQQ705E n852u+d o 2 s E U m 0 ocfififi mfiEEnvSJd ITAQQQQQSHESYQN I 6Q 50 m i EE m-H EEfii Bio S am a n 26 @2 5 E0 2 3:SEmE vQQMW S A m H :Mifimsgas zcfim EEE WmS Q QQ 5 5 o 5 5A m 25 35 QZizS 73 8052 im fi o s 6Q 50 EEE 2 5 ifiw sgs Ea o im E 1 6Q E m E EA m H E EEE EBHid fiifinn ozsmawi 2 w m 28% H1O M .5 m ififi eizgw O O a a 1 m 0% m o m 1 .328? EZ O O m 2v 1323 33. 1| H .........on M5 H10 6Q E E0 EE F EBSJfi E= Q8 w n 82& 00] 6Q m 0 m QE QEE Q o a huqon h so w l. .l Q 50 w fizfifimq 85:63::ni oE Ywo o iw I... ...........o@ 2$ c2 5 E0 ocimt n m o B ES:92 3 wE S iw .IESsQSEwEAN 1 .6 Z ma mas u H 2 2w M 0 13 mm "5 5 F 6Q 50 M I QENNE Q q n wfi o nguim ow ow 6Q m 0 m I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I o N Q J IQE Q w EQ Q N I Q "m0 m I o S mQ hxo w w oho w wfi I 6Q mo m I. @2820 8 25:5 3 SE EO Q I 6Q "m0 m I I QEEB EQEQ Q Qd QEP u I I 6Q "m0 m QEEETEQQEE QQ{a II EQQ Q w Q I on 6Q "mo m 30 ESEM M S QQ o flvain n a 96 .e E W M I. 5Q mo H E8 EQEwE aaE edfio fim i fifl 08 6Q m 0 m I I E QEQ M Qa Nw Qm 2 E E QE SQ am o 6Q 50 m I QES QQfio fl h EQ Q EQ Q i I I EM QQ E EQ Q Q I I I I I I I I I I I I I I d I 6Q 50 m 2 ESEmE h n$5223 m 1E E Q EQ Q Q I I ficofiezavm wfid ow I. NH 6Q "m0 I I @2850 ow E HE Q ow ow I 6Q "m 0 I I Q H EQEQ QE fiim I I ou o I m 6Q "m0 I I 33 27wnoeaobiEE MQEQ {a ow I o I Q WHO 6523bm H B E EH QQO SO E w io oa g I m in. 2K m H fia h wfihxon5Q E= E SQ O m II I I EE Q I o 6Q ED I 2525A m lo iaflcg mo mv w Eo u u vd ou 69 JMO Q S Q 3 2Ewong 5530305 3 ow 4 6Q m0 m I 3 30 Bow 2166a mo m Q5 H RB QEoHo Q w Eo Q N ow I. am E0 m Q E Q 3 8503 Q? E WEE BE QS av n EH Q M Q .I N 0 w I O L O M 6Q m0 m E I I E Q E E QE SQ Q I III I I... I. I. I c I. m #6 m QEE Q 3 o 0329xornaons h wqwn dw SEER 3 "MO m I I @2830 3 oaomswam ao ofi I.

6Q mo 00 E Q E QQ- on E h wiwu o swiu I. 3? N000 m I I I Q S 546565359S wE Q SO Q fi I I. Q 50 m I. IIIIIIIIIIIIIIIIIIIIIII 623 m cs BEQEQE E Q SQ Q +N I.

. l 5 Q MO m I IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII oENQ m ma im a w d IIIIIIIIIIIIIIIIIIIIIIIIIII ou H1O w m o v an E0 m I E3 25% 3:$23 B Q m EE I -Efifie Q m 0 H IIIIIIIIIIIIIIII I I E n EBEFw-oflfiflbb mJEHE i nmaq ho n uiw ou IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII on IIIIIIIIIII I I as 6Q 50 m I I- I I 2 2 2:2?wvm fi wg QH ifim i fimi s:23 I IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII d IIIIIIIIIII I 6Q m0 m E3 QES W v S m mJ Q E Q Q w QEQ II. IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII d 69 "m0 m IIIIIIIIIII I 9 EBEWE R n QENQ QQH EEQ wi na awim EEE EQ Q d o IIIIIIIIII Q "m 0 m IIIIIIIIIIIIIIIIIIIIIIIII I I 23256 m 05Hague?xo wfi ho guim IIIIIIIIIIIIIIIIIIIIIIIIIII ow I I I IIIIIIIIII I I. IIIII II I I 6Q mO m IIIIIIIIIII I I I IIIIIIIIIIIII QSNEMEma fiofla hmwsaeo o mv EQ Q N IIIIIIIIIIIIIIIIIIIIIIIIIII ou I I IIIIIIIIIIIII ow I I Q "m0 m IIIIIIIIIIIIIIIIIIIIIIIIIIIIII QS QE m m o ENE:a xo ofi ho uiu IIIIIIIIIIIIIIIIIIIIIIIIIII ow .I IIIIIIIIIIIIIIIIIIIIIII o IIIIIIIIIII I a Q "m0 m IIIIIIIIIIIIIIIIIIIIIIIIIIIIIII I I 02.630 22. 2Enon58 n SaxQEvQ oS Q I I IIIIIIIIIIIIIIIIIIIII ou I I I I I I I I I I I I I I I I I I I I I I I I I I ow IIIIIIIIII 6Q "m 0 m IIIIIIIII 2 5 E a? woo So flnm wn A; Eno w wa wh s u ncwYm I I IIIIIIIIIIIIIIIIIIIII ow IIIIIIIIIIIIIIIIIIIIIIIIII I I I I ow IIIIIIIIIII I I z: 6Q "mu 0 m I I I I I 2 3 Eo z no c amowA ESS RQ oS umY $1 I I I IIIIIIIIIIIIIIII I I cu IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII ow IIIIIIIIIII I 63 5 m0 IIIIIIII @ESEA m o5E DB Q E QQE F Q w Eo Q Y I IIIIIIIIIII ow IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII I ow IIIIIIIIIIII I Q "m0 IIIIIIIIIIIIIIIIIIIIIIIII Q B O 2 338H Q QQ QUSO G IIIIIIIIIIIIIIIIIIIIIIIIII ou IIIIIIIIIIIIIIIIIIIIIIII III IIIIIIIIIIIII d IIIIIIIIIIII 6Q "m0 QEB Q va 2ES Sg Q NO EQQS O Q IIIIIIIIIIIIIII EQ Q W Q .I

6Q "m0 IIIIIIIIIIIIIIIIIIIIIIIIIIII I I @2850 0 2338505 IIIIIIIIIIIIIIIIIIIIIIIIIII I I 6Q "m0 IIIIIIIIIIIIIIIIIIIIIIIII Q E U va Q QEQQEE Q IIIIIIIIIIIIIIIIIIIIIIIIIII oc I I I 6Q fiwO IIIIIIIIIIIIIIIII I 62320 23 Q QSQBQ Q Q IIIIIIIIIIIIIIIIII I. .o@ m 0 IIIII I I 0S gumfih wa h ofiofiokn m oEo Q IIIIIIIIIIIIIII I I I I I o IIIIIIIIIIIIIIIIIIIII I I 6Q "m O m IIIIIIIIIIIIIIIIIII I I oEuwE QmJ Acfiaflhnmnuhxc wgw muwv w oS v wd I IIIIIIIIIIIII hmosaomsw m IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII ew IIIIIIIIIIII I mm 6Q "mo m IIIIIIIIIIIIIIII E3 E E Y E EA m H 385 E QSS SO Q IIIIIIIIIIIIIIIIIIIIIIIIIIIIIII 96 8 38m IIIIIIIIIS H1 0 w .on m IIIIIIIIIIII 3 2 5 6 3i fi cfidH 05EN aifiHEmE SOEUE Ia IIIIII E Q QQ OG Q O O IIIIIII .62 29.3mm wiwhu 0 @925 "M M 3 6 m m IW W E Q H EH3 Formulae of representative dyes of the foregoing examples are as follows:

EXAMPLE 1 I 01 $0311 H0 /N\ C1C/ C-HN NHOC N=N I N yI-Cl =N 03H EXAMPLE 2 01 110 I N N -SO H HEN-C J-N11 HN-O c N: I

I N K 6?.

no I I 3 EXAMPLE l I\ /i /C1 EXAMPLE 69 Having thus disclosed the invention what I claim is: 1. Reactive dye of the formula wherein R is hydrogen, lower alkyl or chlorine;

R is lower alkyl, COOH, --COO-lower alkyl,

-CONH CO-NH-lower alkyl, -CON(lower alkyl) or CO-NH-lower hydroxyalkyl;

R is lower monoor dihaloalanoyl; lower alkenoyl; lower mono-, dior trihaloalkenoyl; lower alkane-sulfonyloxylower alkanoyl; mono-nuclear arylsulfonyloxy-lower alkanoyl; lower monohaloalkylsulfonyl; lower sulfatoal- 8. The reactive dye according to claim 1 of the formula CH3 N s om 11( I 014 C-HN- NH-OC N=N N iLci N \O/ CH:

References Cited FOREIGN PATENTS 1,139,796 4/1960 France.

CHARLES B. PARKER, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R.

Patent No. 3,542,753 Dated November 24, 1970 Inventor(s) KURT BRENNEISEN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 46, "N should read i Column 2, line 30, "a1" shc read -Cl; line 67, "radical" should read radical,--. Column 3, line "or" should read -or,-; line 68, "halogenoquinoxaline," should read ha quinoXaline,-. Column 6, line 62, "demium" should read -medium--; line 65, "SS-90" should read -8595. Column 8, line 55, in the formula, "Cl should read Cl Column 10, Example 41, in the definition A "4-meth l 2sulfophenyl" should read 4-methyl-2sulfophenyl--. Col Example 6, C should read N Column 16, Example 2, "-50 H Cl should read -S0 H-; Example 7, =N" should read I=N-. Column CH line 72, "dihaloalanoyl" should read --dihaloalkanoyl-; Column 18, Exampl )-SO H" should read SO H--; 62, "dihalophthalazy-" should re Cl dihalophthalazyl- Column 19, line 1, "phenyl" should read phenyl, line 2, "dissulfo-" should read disulfo- Column 20, line 7, "di-dich should read dich1oro.

Signed and sealed this 13th day of March 1973,

(SEAL) Attest:

EDWARD M FLETCHER ,JR. ROBERT GOTTSCHALK Attestlng Officer Commissioner of Pate 

